CN104695012B - Device and method for preparing large-size high-quality graphene single crystal - Google Patents
Device and method for preparing large-size high-quality graphene single crystal Download PDFInfo
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- CN104695012B CN104695012B CN201510128458.XA CN201510128458A CN104695012B CN 104695012 B CN104695012 B CN 104695012B CN 201510128458 A CN201510128458 A CN 201510128458A CN 104695012 B CN104695012 B CN 104695012B
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Abstract
The invention relates to a device and method for preparing a large-size high-quality graphene single crystal. The device comprises a shell and a top cover. The top cover is internally provided with a gas spray head with a gas distributing pipe so that inlet high-purity gas can enter a reaction cavity in an evenly-distributed mode. The reaction cavity is composed of sealed silica pipes, a graphite heating element connected between the two sealed silica pipes in an inserted mode and a graphite crucible placed in the graphite heating element. The graphite crucible is used for containing a SiC wafer substrate. A cooling water system and an intermediate frequency coil are arranged outside the graphite heating element. A gas outlet is formed in the bottom of the shell. The invention further provides the method for preparing the large-size high-quality graphene single crystal on the SiC substrate. By means of the device and method, the migration rate of the high-quality graphene crystal prepared on the SiC substrate is higher than that of graphene prepared through a SiC high-temperature pyrolysis method by 1-2 orders of magnitudes.
Description
Technical field
The present invention relates to a kind of device and method for preparing large-size high-quality Graphene monocrystalline, belongs to Graphene monocrystalline system
Standby device and method technical field.
Background technology
Graphene is with sp by carbon atom2The atom level two dimensional crystal material in hexagonal honeycomb lattice that orbital hybridization is formed
Material, with several high carrier mobilities for decupling commercial silicon chip, and is affected very little by temperature and doping effect, is shown
Excellent electron transport property.Graphene crystal has significant application value in terms of ultra-high frequency electronic device.However, graphite
Serious restriction of the lifting of alkene electronic device performance by quality of graphene, this depends on changing for graphene preparation technology and method
Enter.It is the precondition for currently realizing Graphene application to prepare high-quality, the Graphene crystal of low cost.
CN103643288A discloses a kind of preparation method of high-quality large-size monocrystal graphene, using chemical vapor deposition
Product (CVD) technology, with metals such as copper, platinum as growing substrate, with hydrocarbon as carbon source, is present in the carrier gas containing hydrogen
In the case of, first metallic matrix is heat-treated, and using catalytic pyrolysis under carbon-source gas high temperature, grows single crystal graphene.
Then Graphene is performed etching by regulating and controlling hydrogen and carbon source concentration, reduces the distribution density of single crystal graphene, afterwards again
Adjusting reaction atmosphere makes its regrowth, is so repeated several times, finally obtains high-quality large-size monocrystal graphene.
CN203187782U provides a kind of device for preparing single crystal graphene, it include vavuum pump 1, air inlet 2, exocoel 3,
Heater 4, gas outlet 5, inner chamber 6 and blast pipe 7, it is characterised in that inner chamber is provided with the middle part of exocoel, heater is located at outer
Outside chamber, and at the cavity position, exocoel is respectively arranged at two ends with air inlet and gas outlet, and gas outlet is connected to the one of blast pipe
End, is connected with vavuum pump on blast pipe.Specifically used step is as follows：1), clean sheet metal is placed in inner chamber 6, vacuum is opened
Pump 1, inner chamber 6 form negative pressure, with inert gas by the air emptying in whole cavity.The thermal treatment zone is warmed up to heater 4
More than 1000 DEG C；2), carbonaceous gas, hydrogen and inert gas are passed in cavity, the flow velocity of each gas and the time of ventilation
Depending on the specification of the single crystal graphene that can be prepared as needed；3) all sources of the gas are closed, 4 devices of heating is removed, is closed vavuum pump
1；4), after whole device is cooled to room temperature, sheet metal is taken out, that is, prepares high-quality single crystal graphene.Using this dress
Put and high-quality single crystal graphene can be prepared on the metals such as copper, platinum, the utility model is not only simple in structure, using also compared with
For convenience.
CN102786049A provides the system that SiC pyrolysis methods prepare Graphene, including the gas refining stone as vacuum cavity
Ying Guan, positioned at the SiC substrate in centre position, sensing heating graphite boat and carbon felt heat-insulation layer in vacuum cavity, the SiC substrate position
In graphite boat sample cell, graphite boat is located in the middle part of carbon felt heat-insulation layer, and carbon felt heat-insulation layer is close to the tube wall of vacuum cavity and is formed
Hollow structure；One end of vacuum cavity has vacuum chamber door to open and close vacuum cavity, and the lower section of vacuum chamber door is successively
Be connected with flapper valve, molecular pump and mechanical pump composition vacuumizes gas circuit to carry out vacuum pumping to vacuum cavity on demand；
The other end of vacuum cavity has the infrared acquisition window of the outer glass material of red line.Using the system and method for the present invention, can
High-quality Graphene is prepared with compared with hyperbar state (0.1～1 atmospheric pressure).
From the point of view of reporting at present, the conventional preparation method of Graphene monocrystalline mainly has two big class, and a class is chemical vapor deposition
Product (CVD) method, another kind of is High Temperature SiC pyrolysismethod.CVD method technique is relatively simple, with low cost, but the system of Graphene crystal
Standby to often rely on the metallic substrates such as Cu, Ni or Pt, the Graphene crystal of preparation is peeled off and is transferred to various insulation bases by needs
It is standby on piece.During stripping and transfer, easily Graphene is caused to damage or polluted, this is unfavorable for subsequent electronics
Prepare and performance is improved.High Temperature SiC pyrolysismethod by high temperature make surface of SiC Si atoms depart from SiC substrate come obtain one layer or
Number layer graphene, its production procedure can be blended with current semiconductor process, it is not necessary to which the subsequent technique such as transfer is just expected to do
Into device.But, the uniformity of the Graphene obtained because of the restriction of growth mechanism, SiC pyrolysismethods is poor, it is difficult to which obtaining the number of plies can
There is obvious cushion between the graphene film of control, and the simple Graphene prepared using SiC pyrolysismethods and SiC substrate, drop
The mobility of low Graphene, is unfavorable for the application of graphene electronic device.
The content of the invention
For the problem that above-mentioned prior art is present, the present invention is provided one kind and is made using high temperature CVD technology on sic substrates
The device and growing method of standby large-size high-quality Graphene monocrystalline.
Technical scheme is as follows：
A kind of employing high temperature CVD technology prepares the device of Graphene monocrystalline on sic substrates, and the device includes：
- housing and top cover, top cover are located at housing upper face, have the band gas distribution pipe arranged in air inlet, with top cover in the middle part of top cover
Gas tip connection, be uniformly distributed the high-purity gas of entrance and enter reaction cavity；
- reaction cavity be located at housing central section, reaction cavity by two sections sealed silica envelope, be plugged on two sections sealing quartz
Graphite heater, the graphite crucible composition being placed on inside graphite heater in the middle of pipe, graphite crucible are used to place SiC wafer
Substrate；Reaction cavity is supported by being fixed on the bracing frame of housing inner bottom part；
- cooling water system, it is external positioned at heating graphite, lead to cooling circulating water from bottom to top；
- intermediate frequency coil, it is external positioned at heating graphite, for sensing heating graphite heater；
- gas derivation passage is provided with sealed silica envelope lower end, connect the gas outlet of housing bottom.
The inlet, outlet of this device adopts upper and lower convection type.
According to device of the present invention, it is preferred that the heating graphite has heat insulation layer in vitro；Outside heat insulation layer
It is cooling water system；
According to device of the present invention, it is preferred that the intermediate frequency coil is located at the external cooling water system of heating graphite
Outside.Further preferably, insulation quartz ampoule is additionally provided between cooling water system and heat insulation layer.
According to device of the present invention, it is preferred that housing inner bottom part is fixed on below the cooling water system not
Rust bracing members frame is supported.
According to device of the present invention, it is preferred that pass through adjustable nut or liftable between the top cover and housing
Bolt is connected, and the reaction cavity bracing frame also has height-adjustable nut, by adjusting nut so that including graphite heater
Whole reaction cavity height can adjust up and down；So as to adjust the distribution of the thermal field in reaction cavity, to meet on SiC wafer substrate
Temperature needed for growth Graphene crystal.The bracing frame of the sealed silica envelope lower end is made up of stainless steel material.
The gas inlet and outlet of Graphene preparation facilities of the present invention is located at the upper/lower terminal of reaction cavity, particularly, gas outlet
Lower section have pumped vacuum systems to carry out vacuum pumping to whole body of heater on demand.Pumped vacuum systems is connected with baffle plate in turn
Valve, mechanical pump and molecular pump composition.Can be by prior art.
According to device of the present invention, it is preferred that be provided with infrared temperature measurement device in the gas outlet side of housing bottom.Pass through
Gas from thermal field circulates, and can easily predict the temperature around crystal prototype.
According to device of the present invention, it is preferred that the both ends of the surface of graphite heater are fluted, groove diameter with sealing stone
English pipe diameter is adapted and recess width is adapted with wall thickness of quartz tube, is easy to agree with sealing.
According to device of the present invention, it is preferred that the material of the external heat insulation layer of the heating graphite is carbon felt,
Carbon felt is coated on around graphite heater, fills SiC powder, play preferably function of heat insulation inside heat-insulation layer.
It is in the device of the present invention, it is preferred that top cover and housing are made using identical steel matter, built-in equal in the middle part of top cover
The gas tip of steel, its gas distribution pipe is vertically arranged and internal diameter is 1～2mm.Gas leads to the graphite earthenware for being loaded with SiC wafer substrate
Crucible.The cooling water pipeline of cooling water system is made up of quartz material, leads to cooling circulating water from bottom to top.
In the device of the present invention, the graphite heater is made by high purity graphite (more than 99.99%).In electric current of intermediate frequency
The lower temperature of sensing is raised, it is possible to is obtained higher temperature at short notice, is provided hot environment for graphene growth.
In the device of the present invention, the intermediate frequency coil is made for copper pipe, interior logical cooling circulating water.By prior art it is
Can.Prepare Graphene SiC substrate, preferred 4H-SiC and 6H-SiC chips, using front needing to cut, clean.By prior art
.
Graphite crucible is placed on graphite heater bosom position.The shapes and sizes of graphite heater can be according to required
Thermal field be designed.One more preferably scheme referring to accompanying drawing 2, in the heating graphite body, bottom is cylinder, then past successively
On be bottom heat generating member, middle part heat generating member, upper end preheating lid, the bottom heat generating member carries vent cap, and crucible is placed on down
On portion's heat generating member, it is suitable for reading that the middle part heat generating member blocks crucible, it is to avoid air-flow is injected directly in crucible；The upper end preheats lid
Graphite cover with vent cap.Bottom heat generating member, middle part heat generating member, upper end preheating lid and for high purity graphite (99.99% with
On) material.Structure described herein is only that one kind is illustrated, and the graphite heater of the present invention is not limited to this.
A kind of method for preparing large-size high-quality Graphene monocrystalline on sic substrates, the SiC substrate be 4H-SiC and
6H-SiC chips, including it is as follows using the above-mentioned grower of the present invention, including step：
(1) SiC substrate is put in graphite crucible, the growth of Graphene is carried out on Si faces, height is passed through into reaction chamber
Pure inert gas, in 1～15min react cavity temperature and rise to 800 DEG C, and be incubated 1～5min；Then, in 0.5～6min
1100～1150 DEG C are warmed up to from 800 DEG C and 1～5min is incubated；
(2) high-purity H is passed through into reaction chamber2, from 1100～1150 DEG C of etching temperatures that are rapidly heated, the SiC to high temperature
Substrate is etched, and process conditions are as follows：With the speed of 100～900 DEG C/min, SiC substrate is rapidly heated to 1400～
1600 DEG C, H2Flow is 10～800sccm, and the duration is 10～30min, completes etching；Cut-out H2Air-flow；
(3) SiC substrate after step (2) etching is cooled to into 900 DEG C and less for 100～800 DEG C/min by speed, and
1～5min of insulation, then vacuumizes to cavity, then,
(4) 1400～1700 DEG C are warming up to for 100～800 DEG C/min by speed, 0.5～5min of constant temperature makes surface of SiC
Si-C key sections rupture, and generate C sources nucleating point；Ar gases are passed through, 500～5000sccm of flow is produced to remove surface of SiC cracking
Raw Si atoms；Then,
(5) it is passed through high-purity H2, Ar and carbonaceous gas, the growth of Graphene, H are carried out on the nucleating point position of C sources2, Ar and contain
The volume ratio of carbon gas is 1:1:1～1:10:10, H2, Ar and carbonaceous gas flow controlled in 100～1000sccm respectively,
0.5～10min of constant temperature；Complete the growth of Graphene.Then,
(6) room temperature is down to the rate of temperature fall of 100～900 DEG C/min.
Taking out growth has the SiC substrate of Graphene.
Preferably, step (1) high purity inert gas are the nitrogen or Ar gas or other inert gases of 5N and the above；It is logical
Enter gas flow rate for 400～3000sccm.
In preparation method of the present invention, step (1) is first passed through high purity inert gas and is warmed up to 800 DEG C, to SiC substrate
And prebake conditions inside reaction cavity, are carried out, make the desorbing gas of surface of SiC and inside cavity absorption and discharge cavity, to reach drop
Residual oxygen and vacuum is further lifted in low cavity.Hereafter, 1100～1150 DEG C are warmed up to from 800 DEG C and are incubated,
Heating system can be stablized.
Preferably, step (2) high-purity H2For the 5N and H of the above2.By H2Etching is regular to obtain SiC substrate surface
The atomic stepses structure of arrangement.
Preferably, carbon containing high-purity gas described in step (5) are the CH of 5N and the above4Or C2H6Gas.In this, as outside
Carbon source.Step (6) rate of temperature fall preferably 300～800 DEG C/min.
The present invention relates to a kind of new equipment and new method for preparing Graphene crystal.The equipment is provided with vacuum-control(led) system,
Heated by Medium frequency induction mode, using graphite heater as supplying heat source, special gas are flowed into from gas tip and complete to rise
Control climate and high temperature chemical vapor deposition process in gentle temperature-fall period.The present invention combines CVD growth and SiC extensions
The advantage of high temperature pyrolytic cracking (HTP), with SiC wafer as substrate, by precise control of temperature, makes surface of SiC that cracking reaction to occur, then
The Si atoms on surface are removed, the nucleating point centered on C atoms is formed, after nucleating point temperature is reached, is passed through from outside first containing C
The carbon-source gas of element, realize effective combination of SiC wafer therein carbon source and external carbon source, prepare Graphene two dimension brilliant
Body.As a result of SiC as substrate, there is great advantage in the preparation of subsequent electronics, mobility can also obtain bright
It is aobvious to improve.Using the growing method and technique, can be so that high-quality Graphene crystal be prepared on SiC wafer substrate, which moves
Shifting rate improves nearly 1～2 order of magnitude than simple SiC method for pyrolysis.
The beneficial effect of the Graphene single crystal preparation device and method of the present invention：
1st, device of the invention can pass through to change graphite heater using the graphite material of Medium frequency induction as heater
Shape designing thermal field, so as to effectively adjusting and obtaining the thermal field needed for preparation process.It is fast with temperature rate, work
The features such as temperature is high.
2nd, device of the invention has gas preheating function.Hyperpure gas is passed through after reaction chamber from air inlet port, can be with
Gas preheating is carried out by the duct at the top of designed graphite heater, makes gas advance to the SiC wafer up in reaction chamber
Surface temperature, so as to the temperature fluctuation of SiC wafer in reaction chamber is reduced or avoided, improves Graphene and prepares quality.
3rd, device reaction housing depth of the invention can adjust.The calandria upper and lower ends of high temperature with sealed silica envelope phase
Even, can pass through to adjust the height of metal nuts between its lower end sealed silica envelope and bracing frame, control reaction cavity in
Position in frequency heating coil, designs in combination with the shape of graphite heater, reaches the purpose for adjusting thermal field distribution.
4th, device heat-insulation system of the invention is more preferable.Carbon felt heat-insulation layer is laid between heat-insulated cavity and cooling quartz ampoule,
And SiC powder is filled in carbon felt internal layer, to maintain the heat balance of internal heating system and external insulation system.Meanwhile, SiC powder
The filling of body ensure that the space filling of carbon felt layer between heating cavity and quartz ampoule, adds somewhat to the closed of system
Property.In addition, the filling of SiC powder efficiently avoid the potential pollution that traditional C powder filling brings.
5th, the reaction system of device of the invention adopts high purity graphite crucible to give birth to as the Graphene with SiC wafer as substrate
Long conversion zone, graphite crucible are that external carbon source and internal SiC wafer C atomic nucleation point provide relatively closed reaction sky
Between, the shapes and sizes of graphite crucible are designed according to thermograde situation.In graphite crucible bottom, easily can be divided
The uniform thermal field of cloth, meets requirement of the graphene growth to temperature, uniform so as to surface is obtained in large-size SiC substrate
Graphene crystal.
6th, the method for the present invention is related to one kind using high temperature pyrolytic cracking (HTP) with reference to chemical vapor deposition (CVD) technology, serves as a contrast in SiC
Graphene monocrystalline is prepared by inside and outside carbon source synergistic on bottom, is which in nanometer electronic device, nesa coating, display and solar energy
The application of the photoelectric fields such as battery electrode, gas sensor, thin film electronic device lays the foundation.
Description of the drawings
Fig. 1 is the device structure schematic diagram that the present invention prepares Graphene crystal.Wherein, 1, top cover, 2, cooling water system, 3,
Cooling water system bracing frame, 4, graphite heater, 5, graphite crucible, 6, SiC wafer substrate, 7,8,9 is sealed silica envelope, 10,
Insulation quartz ampoule, 11, intermediate frequency coil, 12, bracing frame, 13, air inlet, 14, gas outlet, 15, heat insulation layer, 16, infrared survey
Warm system, 17, housing.
Fig. 2 is that graphite heater of the present invention splits structure vertical section schematic diagram.Wherein, 18, the preheating of the upper end with passage
Lid, 19, middle part heat generating member, 20, the bottom heat generating member with passage.
Fig. 3 is bell cross section structure schematic diagram of the present invention, and Fig. 4 is bell vertical section structure schematic diagram of the present invention.Wherein,
21st, gas tip.22nd, qi-emitting hole pipeline.23rd, liftable bolt or adjustable nut.
Fig. 5 is graphite heater thermal field distribution (a) of the present invention and graphite crucible surface temperature field distribution map (b).
Fig. 6 is embodiment 2, the Raman spectrogram of Graphene crystal is grown in embodiment 3, and Fig. 7 is embodiment 4 and embodiment 5
The Raman spectrogram of middle growth Graphene crystal, abscissa is Raman shift (cm-1), ordinate is intensity (a.u.).
Fig. 8 is AFM (AFM) photo of the Graphene crystal prepared by embodiment 2.
Fig. 9 is AFM (AFM) photo of the Graphene crystal prepared by embodiment 3.
Figure 10 is AFM (AFM) photo of the Graphene crystal prepared by embodiment 4.
Figure 11 is AFM (AFM) photo of the Graphene crystal prepared by embodiment 5.
Specific embodiment
With reference to embodiment and accompanying drawing, the present invention will be further described, but not limited to this.Height used in embodiment
Pure H25N is not less than with Ar gas purity.
Embodiment 1：A kind of employing high temperature CVD technology prepares the device of Graphene monocrystalline on sic substrates, the device enters,
Gas outlet adopts upper and lower convection type, and structure is as shown in figure 1, carry the top cover 1 of air inlet 13, top in the middle part of above housing 17 being
The gas tip 21 with gas distribution pipe 22 arranged in lid 1 is connected, and is uniformly distributed the high-purity gas of entrance and is entered reaction cavity；Instead
Answer cavity to be located at housing central section, by sealed silica envelope 7,8 and the graphite heater 4 being plugged in the middle of two sections of sealed silica envelopes,
It is placed on the graphite crucible 5 inside graphite heater to constitute, graphite crucible 5 is used to place SiC wafer substrate 6；Reaction cavity leads to
Cross and be fixed on the stainless steel bracing frame 12 of housing inner bottom part and support；There is heat insulation layer 15 outside graphite heater 4；In cooling water system
Insulation quartz ampoule 10 is additionally provided between system 2 and heat insulation layer 15, cooling water system 2 is located at the insulation quartz ampoule of graphite heater
Outside 10, lead to cooling circulating water from bottom to top, below the cooling water system 2, have the stainless steel bracing frame for being fixed on housing inner bottom part
3 support；Intermediate frequency coil 11 is located on the outside of cooling water system 2, for sensing heating graphite heater, in graphite heater, insulation
Heat insulation layer 15 is lined between quartz ampoule also for maintaining the heat balance inside reaction cavity, while strengthening to a certain extent
The seal of system；Quartz ampoule 9 is provided with 8 lower end of sealed silica envelope derives the outlet of 17 bottom of channel connection housing as gas
Mouth 14.Infrared temperature measurement device 16 is provided with 14 side of gas outlet.Circulated by the gas from thermal field, can easily predict crystalloids
Temperature around product.
It is connected by liftable bolt 23 between the top cover 1 and housing；Also have in the stainless steel bracing frame 12 adjustable
The nut of height, by adjusting nut so that whole 4 height of graphite heater can be adjusted up and down；So as to adjust in reaction cavity
Thermal field is distributed, to meet the temperature needed for SiC wafer Grown Graphene crystal.
Embodiment 2：Graphene crystal growth is carried out on 6H-SiC substrates using the device of embodiment 1
1. cutting, cleaned 6H-SiC substrates are put on graphite crucible 5, in reaction chamber, are passed through inert gas Ar gas,
From room temperature to 800 DEG C in 90s, and 90s is incubated, Ar gas throughput is 500sccm.Then it is warmed up to from 800 DEG C in 30s
1150 DEG C and 1150 DEG C be incubated 60s.
2. high-purity H is being passed through toward in reaction cavity so2, while with the speed of 300～600 DEG C/min, be rapidly heated to
1500 DEG C, SiC substrate is etched, H2Flow is 800sccm, and the duration is 15min.
3. the SiC after pair step 2 is etched is cooled to 900 DEG C, rate of temperature fall be 300～800 DEG C/min, here temperature
Degree insulation 5min, while cooling, cuts off H2Air-flow, vacuumizes to cavity.
4. the SiC wafer that pair step 3 is obtained is warming up to 1550 DEG C, and constant temperature 2min again with the speed of 600 DEG C/min, makes
The Si-C key sections fracture of surface of SiC, itself generates C sources nucleating point.Meanwhile, it is passed through substantial amounts of Ar gases, flow 800sccm,
To exclude the Si atoms that surface of SiC cracking is produced.
5. the SiC wafer obtained by pair step 4, is passed through CH4、H2, Ar high-purity gas as external carbon source, formed in step 4
Nucleating point position on carry out the growth of Graphene, CH in mixed gas4、H2, Ar volume ratios be 1:1:10, flow respectively 100,
100th, 1000sccm, constant temperature 3min.
6. the sample obtained by pair step 5 is down to room temperature with the rate of temperature fall of 300～900 DEG C/min.Chip is taken out, is completed
The growth of Graphene crystal is prepared in SiC substrate using inside and outside carbon source synergistic.
Embodiment 3：
As described in Example 2, except that：
In step 1,6H-SiC substrates are put on graphite crucible 5, are passed through in inert gas Ar gas, 90s from room in reaction chamber
Temperature is warmed up to 800 DEG C, and is incubated 90s, and Ar gas throughput is 500sccm.Then 1150 DEG C are warmed up to from 800 DEG C and are protected in 30s
Warm 90s.
In step 2, high-purity H is passed through in reaction chamber2, with the speed of 400 DEG C/min, it is rapidly heated to 1550 from 1150 DEG C
DEG C it is etched, H2Flow is 800sccm, and the duration is 10min.
Step 3 is with embodiment 1.
Step 4：It is brought rapidly up to 1525 DEG C with the speed of 500 DEG C/min, and in this thermostatic 5min, makes surface of SiC
Si-C key sections fracture, obtain growth Graphene carbon source nucleating point.It is passed through substantial amounts of Ar gases, flow 2000sccm, row
Except surface of SiC cracks the Si atoms for producing.
Step 5：It is passed through C2H6、H2, Ar high-purity gas as external carbon source, in the SiC wafer of step 4 it is established into
The growth of Graphene is carried out on epipole position, gas ratio is 1:2:10, flow respectively 50,100,500sccm, constant temperature 3min.
Step 6：Sample obtained by step 5 is down to into room temperature with the rate of temperature fall of 300～900 DEG C/min.Chip is taken out, it is complete
Into the growth of Graphene crystal on sic substrates.
Embodiment 4：Graphene crystal growth is carried out on 4H-SiC substrates using the device of embodiment 1
1. cutting, cleaned 4H-SiC substrates are put on graphite crucible 5, in reaction chamber, are passed through Ar gas inert gases,
From room temperature to 800 DEG C in 90s, and 120s is incubated, Ar gas throughput is 900sccm.1150 are warmed up to from 800 DEG C in 30s
DEG C and be incubated 200s.
2. high-purity H is passed through in reaction chamber2, by SiC substrate with the speed of 600～700 DEG C/min from 1150 DEG C of quick liters
Temperature is etched to 1550 DEG C, H2Flow is 800sccm, and the duration is 10min.
3. the SiC that pair step 2 has been etched carries out being cooled to 900 DEG C, and rate of temperature fall is 500～800 DEG C/min, in this temperature
Insulation 5min, while cooling, cuts off H2Air-flow, vacuumizes to cavity.
4. the SiC wafer that pair step 3 is obtained is warming up to 1500 DEG C again, 300～600 DEG C/min of heating rate, and
1500 DEG C of constant temperature 4min, make the Si-C key sections of surface of SiC rupture, and form the carbon source nucleating point of graphene growth.Then in chamber
Substantial amounts of Ar gases are passed through inside, flow is 3000sccm to exclude the Si atoms that surface of SiC cracking is produced.
5. the SiC wafer obtained by pair step 4, is passed through CH4、H2, the high-purity gas such as Ar as external carbon source, in step 5 shape
Into nucleating point position on carry out the growth of Graphene, gas ratio is 1:5:10, flow respectively 20,100,200sccm, constant temperature
5min。
6. the sample obtained by pair step 5 is down to room temperature with the rate of temperature fall of 300～900 DEG C/min.Chip is taken out, is completed
The growth of Graphene crystal in SiC substrate.
Embodiment 5：As described in Example 4, except that：
Step 1：Cutting, cleaned 4H-SiC substrates are put on graphite crucible 5, high-purity Ar gas etc. in reaction chamber, is passed through
Inert gas, from room temperature to 800 DEG C in 90s, and is incubated 180s, and Ar gas flows are 1000sccm.From 800 in 30s
DEG C it is warmed up to 1150 DEG C and is incubated 180s.
Step 2：Logical embodiment 4.
Step 3：The SiC wafer for having etched is cooled to 900 DEG C, and rate of temperature fall is 300～500 DEG C/min, and in this temperature
Insulation 5min, while cutting off H2Air-flow, vacuumizes to cavity.
Step 4：The SiC wafer obtained by step 3 with the ramp of 400～600 DEG C/min to 1475 DEG C, constant temperature
3min, makes the Si-C key sections of surface of SiC rupture, and itself generates carbon source nucleating point.Substantial amounts of Ar gases are then passed to, flow is
2000sccm, excludes the Si atoms that surface of SiC cracking is produced.
Step 5：The SiC wafer of gained, is passed through C2H6、H2, Ar high-purity gas as external carbon source, it is brilliant in the SiC of step 4
The growth of Graphene, C are carried out on piece on established nucleating point position2H6、H2, Ar gas volume fractions be 1:10:10, flow point
Not Wei 10,100,100sccm, constant temperature 10min.
Step 6：The sample of gained is down to room temperature with the rate of temperature fall of 400～600 DEG C/min.Chip is taken out, is completed in SiC
The growth of Graphene crystal on substrate.
Product checking is tested：
Test experience is carried out to the product of above-described embodiment 2-5.The Graphene that embodiment 2, step described in embodiment 3 are obtained
Crystal Raman spectrogram is as shown in Figure 6.Graphene crystal Raman spectrogram such as Fig. 7 institutes that embodiment 4 and step described in embodiment 5 are obtained
Show.
From the Raman of above-mentioned Fig. 6 and Fig. 7, the 2D peaks and G peaks of the Graphene of four embodiment growths is all it is obvious that logical
Cross the ratio (I at D peaks and G peaks in comprehensive analysis Raman spectrogramG/I2D=0.4～0.8) and 2D peaks half-peak breadth FWHM numerical value,
Obtain growing the number of plies of Graphene at 1～4 layer.Half-peak breadth formula corresponding with the number of plies：(n is stone to FWHM=(- 45 × (1/n))+88
The black alkene number of plies).
From the AFM collection of illustrative plates of above-mentioned Fig. 8-11, Graphene step than more uniform, step width substantially 1～5 μm it
Between, shoulder height less (1～3nm), graphene domain is larger, illustrates that the method combined based on the equipment and inside and outside carbon source is existed
Large-sized SiC wafer Grown has gone out the preferable Graphene of quality.
Contrast test：
Using the method for invention, with CH4Or C2H6External carbon source gas, carries out Graphene under different ratio of gas mixture
The preparation of crystal, has obtained similar result.Table 1 gives the result that Graphene crystal is prepared under different condition, and contrast understands,
It is simple under similarity condition to be difficult to prepare Graphene crystal using SiC high-temperature cracking methods, and combined using inside and outside carbon source
Method can prepare Graphene crystal on SiC, illustrate that external carbon source take part in the growth of Graphene crystal, therefore using biography
System SiC method for pyrolysis prepare Graphene there is a problem of cushion be expected to be improved significantly, the property of corresponding graphene device
Also can be expected to be improved significantly.In addition, the method for the present invention, Graphene crystal preparation temperature is compared with traditional Si C high temperature pyrolytic cracking (HTP)
Low (being contrasted from numbering experiment 4 and experiment 6), it is easier to grow, so as to reduce production cost.
The Comparative result of Graphene crystal is grown under table 1, different condition
In sum, using the graphene growth device of the present invention, and integral high temperature CVD technology and SiC high temperature pyrolytic cracking (HTP)s
Growing technology of the present invention is obtained, the Graphene crystal of large-size high-quality, the method can be prepared on 4H/6H-SiC chips
Compare simple SiC high temperature pyrolytic cracking (HTP)s and prepare Graphene crystal, advantage is notable.
Claims (10)
1. the device of Graphene monocrystalline is prepared in a kind of SiC substrate, and the device includes：
- housing and top cover, top cover are located at housing upper face, have the gas with gas distribution pipe arranged in air inlet, with top cover in the middle part of top cover
Body shower nozzle is connected, and is uniformly distributed the high-purity gas of entrance and is entered reaction cavity；
- reaction cavity be located at housing central section, by sealed silica envelope, the graphite heater being plugged in the middle of two sections of sealed silica envelopes,
The graphite crucible composition being placed on inside graphite heater, graphite crucible are used to place SiC wafer substrate；Reaction cavity is by solid
The bracing frame for being scheduled on housing inner bottom part is supported；
- cooling water system, it is external positioned at heating graphite, lead to cooling circulating water from bottom to top；
- intermediate frequency coil, it is external positioned at heating graphite, for sensing heating graphite heater；
- gas derivation passage is provided with sealed silica envelope lower end, connect the gas outlet of housing bottom.
2. the device of Graphene monocrystalline is prepared as claimed in claim 1, it is characterised in that the heating graphite has insulation in vitro
Thermal insulation layer；It is cooling water system outside heat insulation layer；The intermediate frequency coil is located on the outside of the external cooling water system of heating graphite.
3. the device of Graphene monocrystalline is prepared as claimed in claim 1, it is characterised in that passed through between the top cover and housing
Liftable bolt is connected, and the bracing frame of the sealed silica envelope lower end has height-adjustable nut, by adjusting nut so that whole
Individual graphite heater height can be adjusted up and down.
4. the device of Graphene monocrystalline is prepared as claimed in claim 1, it is characterised in that take out true below the gas outlet
Empty set is united.
5. the device of Graphene monocrystalline is prepared as claimed in claim 1, it is characterised in that in the gas outlet side of housing bottom
It is provided with infrared temperature measurement device.
6. the device of Graphene monocrystalline is prepared as claimed in claim 1, it is characterised in that the external insulation of the heating graphite
The material of thermal insulation layer is carbon felt, and carbon felt is coated on around graphite heater, and SiC powder is filled inside heat-insulation layer.
7. the device of Graphene monocrystalline is prepared as claimed in claim 1, it is characterised in that built-in gas tip in the middle part of top cover, its
Gas distribution pipe is vertically arranged and internal diameter is 1 ~ 2mm, is sprayed at and is loaded with the top of the graphite crucible of SiC wafer substrate.
8. the device of Graphene monocrystalline is prepared as claimed in claim 1, it is characterised in that in the heating graphite body, bottom is
Cylinder, then be up successively bottom heat generating member, middle part heat generating member, upper end preheating lid, the bottom heat generating member carry vent cap,
Crucible is placed on the heat generating member of bottom, and the middle part heat generating member is placed in the stepped land of inwall, and the upper end preheating lid is band
There is the graphite cover of vent cap.
9. a kind of method for preparing large-size high-quality Graphene monocrystalline on sic substrates, the SiC substrate be 4H-SiC and
The device of Graphene monocrystalline is prepared on 6H-SiC chips, including the SiC substrate described in usage right requirement any one of 1-8, including
Step is as follows：
（1）SiC substrate is put in graphite crucible, Si faces up, the growth of Graphene is carried out on Si faces, led to into reaction chamber
Enter high purity inert gas, cavity temperature is reacted in 1 ~ 15min and rise to 800 DEG C, and be incubated 1 ~ 5min；Then, in 0.5 ~ 6min
It is interior that 1100 ~ 1150 DEG C are warmed up to from 800 DEG C and 1 ~ 5min is incubated；
（2）High-purity H is passed through into reaction chamber2, from 1100 ~ 1150 DEG C of etching temperatures that are rapidly heated, the SiC substrate of high temperature is entered
Row etching, process conditions are as follows：With the speed of 100 ~ 900 DEG C/min, SiC substrate is rapidly heated to 1400 ~ 1600 DEG C, H2Stream
Measure as 10 ~ 800sccm, the duration is 10 ~ 30min, complete etching；Cut-out H2Air-flow；
（3）By step（2）SiC substrate after etching is cooled to 900 DEG C and less for 100 ~ 800 DEG C/min by speed, and is incubated 1
~ 5min, then vacuumizes to cavity, then,
（4）1400 ~ 1700 DEG C are warming up to for 100 ~ 800 DEG C/min by speed, 0.5 ~ 5min of constant temperature makes the Si-C keys of surface of SiC
Portion fractures, generate C sources nucleating point；It is passed through inert gas, 500 ~ 5000sccm of flow, to remove what surface of SiC cracking was produced
Si atoms；Then,
（5）It is passed through high-purity H2, Ar and the carbonaceous gas as external carbon source, in step（4）On described C sources nucleating point position
The growth of Graphene, H are carried out under inside and outside portion's carbon source synergistic effect2, Ar and carbonaceous gas volume ratio be 1:1:1~1:10:10,
Mixed gas flow is 100 ~ 800 sccm, 0.5 ~ 10min of constant temperature；Complete the growth of Graphene；Then,
（6）Room temperature is down to the rate of temperature fall of 100 ~ 900 DEG C/min.
10. the method for preparing large-size high-quality Graphene monocrystalline on sic substrates as claimed in claim 9, its feature exist
In step（1）The high purity inert gas are the argon gas or nitrogen of 5N and the above；Be passed through inert gas flow velocity be 400 ~
3000sccm。
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